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Metal Heptafluoroisopropyl (M-hfip) Complexes for Use as hfip Transfer Agents

机译：金属庚二氟异丙基（M-HFIP）配合物，用作氢铅转移剂

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摘要

New coinage-metal heptafluoroisopropyl (L_( n )M-hfip) complexes are synthesized from the metal fluoride and inexpensive hexafluoropropene (M = Ag, Cu; L = PPh_(3), 2,2,6,6-tetramethylpiperidine (Htmp)). Reaction of the silver Htmp complex with a Ni dibromide complex led to efficient hfip transfer to afford L_(2)NiBr(hfip) (L = 2-ethylpyridine). Treatment of the Ni-hfip complex with ZnPh_(2) gave the corresponding L_(2)NiPh(hfip) complexes, which were investigated for reductive elimination of PhCF(CF_(3))_(2). Although the desired reductive elimination proved unsuccessful, addition of carbon monoxide to L_(2)NiPh(hfip) effected an efficient heptafluoroisopropyl carbonylative cross-coupling. Further, while the silver complex does not undergo hfip transfer to organic electrophiles, the copper complex (phen)(PPh_(3))Cu(hfip) ( 3b ) effectively transfers the hfip unit to various substrates. We investigated the scope of 3b with acid chlorides toward the synthesis of perfluoroisopropyl aryl ketones. Additionally, reaction conditions for hfip transfer to p -fluorobenzyl bromide and p -fluorobenzaldehyde were identified. As a bonus, 3b was easily generated on a gram scale using commercially available copper hydride by taking advantage of a rapid hydrodefluorination to generate “Cu–F” in situ. Aspects of the observed reactivity are supported by DFT calculations.
机译：从金属氟化物和廉价的六氟丙烯（M = Ag，Cu; L = PPH_（3），2,2,6,6-四甲基哌啶（HTMP）合成了新的铸造 - 金属庚二丙基（L_（N）M-HFIP）配合物。 ）。银HTMP络合物与Ni二溴化物复合物的反应LED以有效的氢屈湿转移，得到L_（2）NiBri（HFIP）（L = 2-乙基吡啶）。用ZnPH_（2）处理Ni-HFIP络合物，得到了相应的L_（2）NIPH（HFIP）复合物，用于还原用于还原消除PHCF（CF_（3））_（2）。虽然所需的还原消除证明是不成功的，但加入一氧化碳至L_（2）NIPH（HFIP）的羰基交联偶联的有效庚二丙基丙二丙基。此外，虽然银络合物不经历HFIP转移到有机电泳，但铜络合物（PP）（PPH_（3））Cu（HFIP）（3b）有效地将氢纤维单元转移到各种基材上。我们研究了酰氯朝向全氟异丙基芳基酮的合成的3B的范围。另外，鉴定了HFIP转移的反应条件至对氟苄基溴和对氟苄醛的反应条件。作为奖励，通过利用可商业上可获得的氢化物通过利用快速的水分解以产生“Cu-F”原位产生3b，以便在克革术中容易地产生3B。观察到的反应性的方面由DFT计算支持。

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  • 来源
    《Organometallics》 |2018年第3期|共11页
  • 作者

    Nicholas O. Andrella; Karen Liu; Bulat Gabidullin; Monica Vasiliu; David A. Dixon; R. Tom Baker;

  • 作者单位

    Department of Chemistry and Biomolecular Sciences and Center for Catalysis Research and Innovation University of Ottawa Ottawa Ontario K1N 6N5 Canada;

    Department of Chemistry and Biomolecular Sciences and Center for Catalysis Research and Innovation University of Ottawa Ottawa Ontario K1N 6N5 Canada;

    Department of Chemistry and Biomolecular Sciences and Center for Catalysis Research and Innovation University of Ottawa Ottawa Ontario K1N 6N5 Canada;

    Department of Chemistry The University of Alabama Tuscaloosa Alabama 35487 United States;

    Department of Chemistry The University of Alabama Tuscaloosa Alabama 35487 United States;

    Department of Chemistry and Biomolecular Sciences and Center for Catalysis Research and Innovation University of Ottawa Ottawa Ontario K1N 6N5 Canada;

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  • 中图分类 元素有机化合物;
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